Nitroxyl-mediated oxidation of lignin and polycarboxylated products

Title: Nitroxyl-mediated oxidation of lignin and polycarboxylated products

Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on .beta.-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric .beta.-hydroxy acid. The polymeric .beta.-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The .beta.-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

Inventors:: Stahl, Shannon S.; Rafiee, Mohammad

Issue Date:: 2018-02-27

OSTI Identifier:: 1423443

Assignee:: WISCONSIN ALUMNI RESEARCH FOUNDATION (Madison, WI) CHO

Patent Number(s):: 9,903,028

Application Number:: 15/167,053

Contract Number:: FC02-07ER64494

Resource Relation:: Patent File Date: 2016 May 27

Research Org:: Chicago Operations Office, Argonne, IL (United States)

Sponsoring Org:: USDOE

Country of Publication:: United States

Language:: English

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Works referenced in this record:

Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin
journal, April 2013

Rahimi, Alireza; Azarpira, Ali; Kim, Hoon
Journal of the American Chemical Society, Vol. 135, Issue 17, p. 6415-6418
DOI: 10.1021/ja401793n

Lignin Biosynthesis
journal, June 2003

Boerjan, Wout; Ralph, John; Baucher, Marie
Annual Review of Plant Biology, Vol. 54, Issue 1, p. 519-546
DOI: 10.1146/annurev.arplant.54.031902.134938

Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems.
journal, April 1964

Nicholson, R. S.; Shain, Irving
Analytical Chemistry, Vol. 36, Issue 4, p. 706-723
DOI: 10.1021/ac60210a007

The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010

Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
DOI: 10.1021/cr900354u

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